JP2010027346A - Insulating material component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulating material component comprising a polyalkylene terephthalate resin composition capable of restraining a flame retardant from bleeding out, without adding a halogen flame retardant, and satisfying electrical safety such as a glow wire property and a tracking property of Revised IEC 60335-1 Standard. <P>SOLUTION: This insulating material component has a resin molded part formed using the polyalkylene terephthalate resin composition blended with at least (A): (A-1) 99-50 wt.% of polyalkylene terephthalate resin, (A-2) 1-40 wt.% of polystyrene resin, and (A-3) 1-10 wt.% of compatibilizer, per 100 pts.wt. of resin composition having a constitutive ratio hereinbefore, (B): 50-130 pts.wt. of total amount of flame retardant combination component comprising (B-1) 25-55 pts.wt. of phosphate flame retardant, (B-2) 30-70 pts.wt. of nitrogen flame retardant comprising a salt of amino group containing triazine, (B-3) 1-20 pts.wt. of metal borate, and (B-4) 0.5-10 pts.wt. of fluororesin, and (C): 0-20 pts.wt. of inorganic filler, and containing respectively 1 wt.% or less of polyphenylene ether resin, polyphenylene sulfide resin, phenol resin and red phosphorous, and the resin molded part supports directly a connection part through which a rated current exceeding 0.2 A flows, or is located within 3 mm or less of distance from the connection part. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to an insulating material component mainly composed of a polyalkylene terephthalate resin and excellent in flame retardancy and electrical safety. Specifically, it is a resin composition using a non-halogen flame retardant, and is molded using a polyalkylene terephthalate resin composition having excellent glow wire characteristics in addition to flame retardancy and tracking resistance. It relates to an insulating material part having no flame retardant bleed-out.

In recent years, demands for electrical safety in electrical and electronic parts are becoming higher than before. For example, according to the recently revised IEC 60335-1 standard of the International Electrotechnical Commission (IEC), in household electrical products such as refrigerators and fully automatic washing machines, Among the components, insulating material components that support connections through which current exceeding 0.2 A flows during normal operation, and electrical insulating material components that are within a distance of 3 mm from these connections (printed circuit boards, terminals) The material of the base, plug, etc. is that the Glow-wire Ignition Temperature (Glow-wire Flammability Index, abbreviated as GWFI value) is 1.5 mm thick and 850 ° C or higher. (Abbreviation: GWIT value) must be satisfied that the thickness is 0.8 to 3 mm and is 775 ° C. or higher. More desirably, the GWFI value is 960 ° C. or higher, and the GWIT value is 800 ° C. or higher at a thickness of 0.8 to 3 mm.

Of course, these parts are already required for similar electrical and electronic parts. Underwriters Laboratories Inc. UL-94 standard flame resistance and tracking index (abbreviation) CTI) or Proof Tracking Index (abbreviated as PTI) must be met at the same time. That is, it is necessary to satisfy flame retardancy of V-2 or more at a thickness of 0.8 mm and 550 V or more in PTI (or CTI). Preferably, it is V-0 and is 600V or more.

In this way, in addition to flame retardancy and tracking resistance, strict regulations are provided for resistance to ignition and flame propagation, that is, electrical safety, and parts that satisfy all requirements in a well-balanced manner are required.

By the way, polyester resins, especially polybutylene terephthalate resin (hereinafter sometimes abbreviated as “PBT resin”) and polyethylene terephthalate resin (hereinafter sometimes abbreviated as “PET resin”) are mechanical properties. Due to its excellent electrical properties and heat resistance, it has recently been used in many applications such as electrical equipment parts and machine parts. In particular, since excellent flame retardancy is easily obtained and at the same time excellent mechanical properties, it is also used as an insulating material for parts of electrical and electronic equipment that operate without the above-mentioned operator. I came.

It is well known that when a halogen-based flame retardant is blended with a polyester resin such as PBT resin, V-0, which is the highest evaluation in the UL-94 standard, can be reached. Here, the flame retardancy of the UL-94 standard known as flame retardancy evaluation (hereinafter simply referred to as “flame retardance”) refers to resistance such as tracking characteristics and glow wire characteristics (hereinafter referred to as “electricity”). "Safety") is an index that is evaluated in a completely different way. That is, the flame retardancy of UL-94 indicates “incombustibility” when a burner flame is brought into contact, whereas the GWFI value and GWIT value are defined in the revised IEC 60335-1 standard, It is an index that evaluates ignitability at high temperatures due to, and exhibits completely different properties. Moreover, even if it is V-0, which is the highest evaluation in the UL-94 standard, the electrical safety may be insufficient, and conversely, even if V-2 is less flame retardant than V-0, Since there is a case where high electrical safety is shown, electrical safety cannot be predicted from existing technical contents in which only the evaluation of flame retardancy of UL-94 is shown.

Patent Documents 1 and 2 disclose a polyester resin composition excellent in electrical safety using a halogen-based flame retardant. The document shows that these polyester resin compositions pass the IEC 60335-1 standard for GWFI values and GWIT values at a thickness of 3 mm.
However, in recent years, because of concerns over adverse environmental impacts, such as incineration, for disposal after use of molded products using halogenated flame retardants, insulating material parts made of polyester resin compositions that do not use halogenated flame retardants Is required. As flame retardants other than halogen flame retardants for polyester resins, phosphate ester flame retardants are widely used. For example, Patent Document 3 includes (A) 95 to 30 parts by weight of a polyester resin, (B) 5.0 to 70 parts by weight of a polyphenylene ether resin and / or a polyphenylene sulfide resin, and a component (A) and a component ( B) For a total of 100 parts by weight, (C) 0.05-10 parts by weight of compatibilizer, (D) 2.0-45 parts by weight of phosphate ester compound or phosphonitrile compound, (E) reinforcing filler 0 -150 parts by weight, (F) 0.001-15 parts by weight of an anti-dripping agent, (G) 0-45 parts by weight of melamine cyanurate, (H) 0-15 parts by weight of a polystyrene resin containing an epoxy group (however, In the case where the component (B) is less than 35 parts by weight, a flame retardant polyester resin composition containing a component (G) of 0.5 to 45 parts by weight is disclosed. The patent document discloses flame retardancy, hydrolysis resistance, plate-out (gas components such as resins and additives adhere to the mold during molding, and the additives have poor compatibility with the resin components after molding. Therefore, there is no description of electrical safety. In addition, various compounds such as (F) anti-dripping agents such as layered silicates and fluorine-containing polymers are disclosed. Of the 30 examples described in the examples, 28 examples are layered silicates. Only one example uses a fluorine-containing polymer. The blending amount of the fluorine-containing polymer is as small as 0.05 parts by weight with respect to 100 parts by weight of the total amount of PBT and PPE. Furthermore, although the clear description is not admitted about the compounding purpose of the polystyrene resin containing the epoxy group which is 1 type of the polystyrene resin of (H) component of the said invention, Example 1 and Examples 28-30 are not recognized. From the comparison, it is judged that the mechanical strength and the hydrolysis resistance are effective. In other words, this document does not have any description or suggestion about improving the tracking property or the glow wire property.

Furthermore, in Patent Document 4, (A) 100 parts by weight of polybutylene terephthalate resin or 100 parts by weight of polybutylene terephthalate resin and polyethylene terephthalate resin, (B) 1 to 100 parts by weight of epoxy-modified styrene resin, (C) 1 to 100 parts by weight of a phosphate ester and (D) 1 to 150 parts by weight of a salt of a triazine compound and cyanuric acid or isocyanuric acid, and 5 weights of polyphenylene ether and polyphenylene sulfide A flame retardant polybutylene terephthalate resin composition containing no more than 1 part is disclosed. Further, the document describes that the blending amount is less than 5 parts by weight because blending of polyphenylene ether and polyphenylene sulfide brings about a decrease in mechanical strength and color tone. In particular, in the examples of this document, these components are blended at a ratio of 1.5 parts by weight with respect to 100 parts by weight of the polyester resin component. In the said invention, although there is no description about glow wire property, about tracking property, in the paragraph number 0143 of this literature, "By adding the ethylene copolymer or talc of Examples 15-16, tracking resistance ( According to the test method shown in the IEC Publication 112 standard, the breakdown voltage (V) at which the insulation of the molded product is broken is improved, and the larger the breakdown voltage is, the better the breakdown voltage is from less than 600 V to the breakdown voltage of 600 V or more. It was found that a molded article having excellent electrical characteristics could be obtained, but the flame retardance was slightly reduced in the case of an ethylene copolymer. " This indicates that only those blended with an ethylene copolymer or talc showed a tracking property of 600 V or more, indicating that the ethylene copolymer or talc is a factor for adjusting electrical characteristics. . Furthermore, although there is a description that the flame retardancy of the ethylene copolymer is lowered, a decrease in mechanical strength is recognized when compared with Example 16 in which talc is blended and Example 6 in which talc or the like is not blended. . That is, the technique described in this document shows that it is quite difficult to achieve 600 V, which is a desirable target of tracking performance, while maintaining mechanical strength.
In the present invention, except for one example, 25 parts by weight of polystyrene resin, 40 parts by weight of phosphate ester, and 40 parts by weight of melamine cyanurate are blended with respect to 100 parts by weight of polyester resin. In a special example (Example 10), the amount of melamine cyanurate is increased to 50 parts by weight. Moreover, in the said literature, although the fluororesin is not an essential component, it is used in many Examples. Further, paragraph number 0084 of the document has a description of a flame retardant other than a fluororesin or a flame retardant aid, but only a variety of materials are listed, and no specific effects are described. It has not been.

Patent Document 5 includes (A) 20 to 60% by weight of a thermoplastic polyester resin, (B) 1.0 to 30% by weight of a vinyl resin (polystyrene resin, polymethyl methacrylate resin), and (C) organic. A composition comprising 0.5 to 20% by weight of a phosphorus-based flame retardant, (D) 5 to 50% by weight of glass fiber, and (E) 4 to 20% by weight of a melamine / cyanuric acid adduct is shown. In the present invention, there is a description that a flame retardant such as red phosphorus or a flame retardant aid may be blended for further improvement of flame retardancy. Three examples contain red phosphorus. In addition, these data show that it is difficult to make a polyester resin blended with a vinyl resin difficult with an organophosphorus flame retardant and a melamine / cyanuric acid adduct alone. The evaluation of flammability is 1.6 mm (1/16 inch) in thickness, and it is predicted that it is difficult to achieve V-0 at 0.8 mm (1/32 inch). In addition, (B) vinyl resin is used for the purpose of reducing the thermal conductivity of the composition and for the purpose of suppressing changes in the appearance of the molded product and the surface property of the molded product under high temperature and high humidity. However, it is also described that effects such as improvement of fluidity of the composition can be obtained. However, in Comparative Example 5 of the present invention, a liquid bleedout product is generated despite the blending of polystyrene, and whether or not the change in the surface property of the molded product is suppression of bleedout. It is unknown.

As described above, the blending of the polystyrene-based resin is carried out for the purpose of improving flame retardancy, mechanical strength, hydrolysis resistance, and molded article surface properties. Is not allowed.

JP 2005-232410 A JP 2006-45544 A JP-A-10-77396 JP 2002-294049 A Japanese Patent Laid-Open No. 2000-212412

As a result of intensive studies to solve the above problems, the present inventors have found that the GWIT value does not pass at a thickness of 1.5 mm or less in the polyester resin compositions described in Patent Document 1 and Patent Document 2. . In addition, in the resin compositions described in Patent Document 3 and Patent Document 4, polyphenylene ether resin and / or polyphenylene sulfide resin are essential components, but according to the study by the present inventors, the tracking characteristics are significantly reduced. I found out that Furthermore, it has been found that the composition of red phosphorus as described in Patent Document 5 has a problem of lowering the tracking characteristics and the color tone. In addition, in order to improve the flame retardancy of phosphorus-based flame retardants, there are many examples in which polyphenylene ether resins and phenol resins are blended. As a result of studies by the present inventors, polyphenylene ether resins, phenol resins, red It has been found that when phosphorus is added, the tracking characteristics are drastically lowered. That is, it has been found that a resin composition containing these is not suitable as an insulating material part, and it is necessary to develop an insulating material part that does not substantially contain a polyphenylene ether resin, a phenol resin, or red phosphorus. In addition, there is a problem in identifying the parts when assembling the molded parts, such as the color tone of the molded product containing red phosphorus being limited to red.

An object of the present invention is to solve the above-mentioned problem, satisfying the electrical safety such as the glow wire property and tracking property of the revised IEC 60335-1 standard, and without including a halogen-based flame retardant. An object of the present invention is to provide an insulating material part comprising a polyalkylene terephthalate resin composition in which bleeding out is suppressed. Furthermore, it is providing the insulating material component which can be used for a contact electrical and electronic component.

Based on the above problems, as a result of intensive studies by the present inventors, a specific amount of a phosphorus-based flame retardant and a nitrogen-based flame retardant, which are said to have little flame-retardant effect, are blended, and at the same time, a polystyrene resin is blended. The molded product of the polyalkylene terephthalate resin composition obtained by this method has unexpectedly required characteristics of strict standards related to electrical equipment such as GWIT value, GWFI value, and PTI (revised IEC 60335-1 standard), and It has been found that it can be used as an insulating material part in which the flame-out of the flame retardant is suppressed. Moreover, it discovered that it could be used for a contacted electrical and electronic component by making PBT of a specific terminal carboxyl group and residual tetrahydrofuran amount into a base main component. Specifically, it was achieved by the following means.

(1) (A) For 100 parts by weight of a resin component having the following composition ratio,
(A-1) Polyalkylene terephthalate resin 99-50% by weight
(A-2) Polystyrene resin 1 to 40% by weight
(A-3) Compatibilizer 0-10% by weight
(B) The total amount of the following flame retardant combination component is 50 to 130 parts by weight and (B-1) 25 to 55 parts by weight of a phosphoric ester-based flame retardant (B-2) a nitrogen system comprising a salt of an amino group-containing triazine Flame retardant 30 to 70 parts by weight (B-3) Boric acid metal salt 1 to 20 parts by weight (B-4) Fluorine resin 0.5 to 10 parts by weight (C) Inorganic filler 0 to 200 parts by weight And a resin molded part formed using a polyalkylene terephthalate resin composition in which the content of any of polyphenylene ether resin, polyphenylene sulfide resin, phenolic resin and red phosphorus is 1% by weight or less. Insulating material part characterized in that the molded part directly supports the connection parts through which a rated current exceeding 0.2 A flows or is within a distance of 3 mm from these connection parts .
(2) In the (B) flame retardant combination, the composition ratio (weight ratio) of (B-1) phosphate ester flame retardant and (B-2) nitrogen flame retardant is (B-1) / (B-2). ) = 0.14 to 1.1, The insulating material component according to (1).
(3) The insulating material component according to (1) or (2), wherein the main component of the (A-1) polyalkylene terephthalate resin is a polybutylene terephthalate resin.
(4) (A-2) The insulating material component according to any one of (1) to (3), wherein the polystyrene-based resin includes an epoxy-modified polystyrene-based resin.
(5) (A-1) The main component of the polyalkylene terephthalate resin is a polybutylene terephthalate resin having a terminal carboxyl group amount of 30 eq / t or less and a residual tetrahydrofuran amount of 300 ppm or less. The insulating material component according to any one of (1) to (4).
(6) The insulating material component according to any one of (1) to (5), wherein the resin molded portion has a thin portion having a thickness of 2 mm or less.
(7) Any of (1) to (6), wherein the resin molded portion has a thin portion having a thickness of 2 mm or less, and the insulating material component having the connection portion is disposed in contact with the resin forming portion. The insulating material part according to 1.
(8) The insulating material component according to any one of (1) to (7), wherein the insulating material component has a plate shape.
(9) The insulating material part according to any one of (1) to (8), wherein the connection portion is a contact point.
(10) (A-1) The main component of the polyalkylene terephthalate resin is a polybutylene terephthalate resin having a terminal carboxyl group amount of 30 eq / t or less and a residual tetrahydrofuran amount of 300 ppm or less. The insulating material part according to (9).
(11) Any one of (1) to (10), wherein the insulating material component is a contact electrical / electronic component selected from the group consisting of a relay, a switch, a connector, a sensor, an actuator, a microswitch, a microsensor, and a microactuator. The insulating material part according to 1.

Insulating material parts for electrical and electronic equipment according to the present invention have improved resistance to ignition and flame propagation during operation, and are parts of equipment that operate without an operator, and are in normal operation. In the insulating material parts that support the connection portions where the current exceeding 0.2A flows, that is, the rated current exceeds 0.2 A, and the electrical insulation material components within a distance of 3 mm from these connection portions Can be used widely.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified. Further, in the case of a group having a limited number of carbons, the number of carbons means a number including the number of carbons that the substituent has.

The (A) resin component of this invention is comprised from the below-mentioned (A-1) polyalkylene terephthalate resin, (A-2) polystyrene resin, and (A-3) compatibilizer.

(A-1) Polyalkylene terephthalate resin In the present invention, (A-1) polyalkylene terephthalate resin means that terephthalic acid accounts for 50 mol% or more of all dicarboxylic acid components, and ethylene glycol or 1,4-butanediol is A resin occupying 50% by weight or more of the total diol. The terephthalic acid preferably accounts for 80 mol% or more of the total dicarboxylic acid component, and more preferably 95 mol% or more. More preferably, ethylene glycol or 1,4-butanediol accounts for 80 mol% or more of the total diol component, and more preferably 95 mol% or more. In the present invention, a polybutylene terephthalate resin homopolymer, a polyethylene terephthalate resin homopolymer, or a mixture thereof is preferably used.

The intrinsic viscosity of the polyalkylene terephthalate resin is usually 0.50 or more when measured at a temperature of 30 ° C. using a mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (weight ratio). Preferably, it is 0.6 or more. On the other hand, the upper limit is usually 3.0 or less, preferably 1.5 or less. By setting the intrinsic viscosity to 0.50 or more, the mechanical strength can be improved, and by setting the intrinsic viscosity to 3.0 or less, molding becomes possible. As the polyalkylene terephthalate resin used in the present invention, two or more kinds of polyalkylene terephthalate resins having different intrinsic viscosities may be used in combination.

Examples of dicarboxylic acid components other than terephthalic acid include phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, and 4,4′-diphenoxy. Aromatic dicarboxylic acids such as ethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid 1 Aliphatic dicarboxylic acids such as acids, aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, lower alkyl or glycol esters, etc. You may use a seed | species or 2 or more types together.

Examples of diol components other than ethylene glycol or 1,4-butanediol include diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5 -Aliphatic diols such as pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1 , 4-cyclohexane dimethylol and other alicyclic diols, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, etc. These aromatic diols may be used alone or in combination of two or more.

In the present invention, a hydroxycarboxylic acid such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid, alkoxycarboxylic acid, etc. Monofunctional components such as acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, tert-butylbenzoic acid, benzoylbenzoic acid, tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane Trifunctional or polyfunctional components such as trimethylolpropane, glycerol and pentaerythritol can be used as the copolymerization component.

In order to produce a polyalkylene terephthalate comprising the dicarboxylic acid or derivative thereof and a diol, any method is employed. For example, it is roughly classified into a direct polymerization method in which terephthalic acid and glycol are directly esterified and a transesterification method in which dimethyl terephthalate is used as a main raw material. The former is different in that water is produced in the initial esterification reaction, and the latter is produced in the initial transesterification reaction. The direct esterification reaction is advantageous from the viewpoint of raw material costs.

Moreover, the production method of polyalkylene terephthalate is roughly divided into a batch method and a continuous method, depending on the raw material supply or polymer discharge form. The initial esterification reaction or transesterification reaction is carried out in a continuous operation, and the subsequent polycondensation is carried out in a batch operation. Conversely, the initial esterification reaction or transesterification reaction is carried out in a batch operation, followed by polycondensation. There is also a method of performing the above in a continuous operation.

A preferred embodiment of the (A-1) polyalkylene terephthalate resin used in the present invention has a polybutylene terephthalate resin alone or a polybutylene terephthalate resin as a main component, specifically, (A-1) 50 weight in polyalkylene terephthalate. % Or more is a mixture with polyethylene terephthalate resin in which polybutylene terephthalate is used. The (A-1) polyalkylene terephthalate resin used in the present invention preferably has a terminal carboxyl group amount of 30 eq / t or less and a residual tetrahydrofuran amount of 300 ppm (weight ratio) or less.
In particular, the main component of the (A-1) polyalkylene terephthalate resin is a polybutylene terephthalate resin having a terminal carboxyl group amount of 30 eq / t or less and a residual tetrahydrofuran amount of 300 ppm or less. When the connection part supported by the part is a contact, corrosion of the contact part and accumulation of carbide in the contact part can be prevented, which is preferable.

The amount of terminal carboxyl groups of the polybutylene terephthalate resin can be determined by dissolving PBT in an organic solvent and titrating with an alkali hydroxide solution. In the present invention, the hydrolysis resistance of PBT can be improved by setting the terminal carboxyl group amount to 30 eq / t or less. Since the carboxyl group in PBT acts as an autocatalyst for the hydrolysis of polybutylene terephthalate, if a terminal carboxyl group exceeding 30 eq / t is present, the hydrolysis starts early, and the generated carboxyl group becomes an autocatalyst. In some cases, hydrolysis proceeds in a chain and the polymerization degree of PBT may rapidly decrease. However, by setting the amount of terminal carboxyl groups to 30 eq / t or less, even under high temperature and high humidity conditions, Can be more effectively suppressed.

The residual tetrahydrofuran amount in the (A-1) polyalkylene terephthalate resin, particularly polybutylene terephthalate resin, preferably used in the present invention is 300 ppm (weight ratio) or less, more preferably 200 ppm (weight ratio) or less. . The amount of residual tetrahydrofuran can be determined by immersing the PBT pellets in water, treating at 120 ° C. for 6 hours, and quantifying the amount of tetrahydrofuran eluted in water by gas chromatography. By setting the amount of residual tetrahydrofuran in PBT to 300 ppm (weight ratio) or less, when the insulating material component of the present invention is used at a high temperature, the generation of organic gas is reduced and the risk of corrosion of electrical contacts is further reduced. Tend. If the amount of residual tetrahydrofuran exceeds 300 ppm (weight ratio), the generation of organic gas when the molded product is used at a high temperature increases, which may cause corrosion of the metal. The lower limit of the residual tetrahydrofuran amount is not particularly limited, but is usually about 50 ppm (weight ratio). A smaller amount of residual tetrahydrofuran tends to reduce the generation of organic gas, but the residual amount and the amount of gas generated are not necessarily proportional, and the presence of about 50 ppm of tetrahydrofuran does not pose a problem for normal use. Rather, the presence of a small amount of diol is known to suppress corrosion of electrical contacts (Japanese Patent Laid-Open No. 8-20900), and similar effects are expected for tetrahydrofuran.

(A-1) The polyalkylene terephthalate resin is contained in the resin component (A) in an amount of 50 to 99% by weight, preferably 55 to 99% by weight, more preferably 60 to 99% by weight.

(A-2) Polystyrene resin As the (A-2) polystyrene resin of the present invention, an aromatic vinyl monomer alone or a copolymer, an aromatic vinyl monomer, a vinyl cyanide monomer, and Copolymer composed of at least one selected from rubber components (for example, copolymer of aromatic vinyl monomer and vinyl cyanide monomer, and aromatic vinyl monomer grafted to rubber component) A copolymerized polymer, an amorphous rubber-like polymer in which an aromatic vinyl monomer and a vinyl cyanide monomer are graft-copolymerized on a rubber component, etc.) are used.

Examples of aromatic vinyl monomers include styrene and alkylstyrene (for example, vinyl toluenes such as o-, m-, and p-methylstyrene, vinylxylenes such as 2,4-dimethylstyrene, ethylstyrene, p- Examples include alkyl-substituted styrenes such as isopropyl styrene, butyl styrene, and p-tert-butyl styrene) and α-alkyl substituted styrenes (eg, α-methyl styrene, α-ethyl styrene, α-methyl-p-methyl styrene, etc.). it can. These styrenic monomers can be used alone or in combination of two or more. Of these styrenic monomers, styrene, vinyltoluene, α-methylstyrene and the like are particularly preferable.

Examples of the vinyl cyanide monomer include (meth) acrylonitrile. Vinyl cyanide monomers can also be used alone or in combination of two or more. A preferred vinyl cyanide monomer is acrylonitrile.

Examples of the rubber component include conjugated diene rubber (polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, etc.), olefin rubber ( Examples include ethylene-propylene rubber (EPDM rubber), ethylene-vinyl acetate copolymer, halogenated polyolefin (such as chlorinated polyethylene), and acrylic rubber. These rubber components may be hydrogenated products. These rubber components can be used alone or in combination of two or more. Of these rubber components, conjugated diene rubbers are preferred. In the rubber component such as conjugated diene rubber, the gel content is not limited at all. The rubber component can be produced by a method such as emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, solution-bulk polymerization, bulk-suspension polymerization.

The aromatic vinyl monomer may be used in combination with another copolymerizable monomer. Examples of the copolymerizable monomer include (meth) acrylic acid esters (for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, (Meth) acrylic acid hexyl, (meth) acrylic acid octyl, (meth) acrylic acid 2-ethylhexyl (meth) acrylic acid C _1-18 alkyl ester, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic Hydroxyl group-containing (meth) acrylates such as 2-hydroxypropyl, glycidyl (meth) acrylate, etc.), carboxyl group-containing monomers (for example, (meth) acrylic acid, crotonic acid and other unsaturated monocarboxylic acids, maleic anhydride Aliphatic unsaturated dicarboxylic acids such as acid, maleic acid, fumaric acid and itaconic acid, maleic acid monoester (Monoalkyl maleate, monoethyl maleate, monobutyl maleate, etc., monoesters having 1 to 10 carbon atoms, such as unsaturated dicarboxylic acid monoesters such as fumaric acid monoester, etc.), maleimide series Examples thereof include N-alkylmaleimide such as maleimide and N-methylmaleimide, N-phenylmaleimide and the like. These copolymerizable monomers can be used alone or in combination of two or more. Preferred copolymerizable monomers include (meth) acrylic acid esters (particularly methyl methacrylate), (meth) acrylic acid, maleic anhydride, maleimide monomers and the like.

When other copolymerizable monomer is used, the ratio (weight ratio) between the aromatic vinyl monomer and the other polymerizable monomer is: aromatic vinyl monomer / other copolymerizable monomer And usually 100/0 to 10/90, preferably 95/5 to 10/90, and more preferably 80/20 to 20/80. The more aromatic vinyl monomer is, the greater the bleed-out suppression effect of the flame retardant is. On the other hand, although related to the degree of dispersion of the polystyrene-based resin, if there is a large amount of the aromatic vinyl monomer, carbonization tends to occur, and the tracking property and the glow wire characteristic tend to deteriorate. Preferably it is 80 weight% or less.

More specifically, when a vinyl cyanide monomer is used as a copolymerization component, the aromatic vinyl monomer and the vinyl cyanide monomer (weight ratio) are, for example, an aromatic vinyl monomer Body / vinyl cyanide monomer, usually 10/90 to 90/10, preferably 20/80 to 80/20.

When the rubber component is used, the ratio (weight ratio) between the rubber component and the aromatic vinyl monomer is, for example, rubber component / aromatic vinyl monomer = 5/95 to 80/20, preferably rubber component / aromatic. Group vinyl monomer = 10/90 to 70/30. When the ratio of the rubber component is too small, the impact resistance of the resin composition is lowered. When the ratio is too large, the dispersion becomes poor and the appearance is easily impaired.

Preferred styrene resins include polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), impact-resistant polystyrene (HIPS), graft polymer [acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile- Acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin), acrylonitrile-ethylene-propylene rubber-styrene copolymer (AES resin), acrylonitrile-butadiene rubber-methacrylic acid Methyl-styrene copolymer (ABSM resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), etc.], block copolymer [for example, styrene-butadiene-styrene (SBS) copolymer, styrene -Isoprene-styrene (SIS) copolymer, styrene-ethylene-butylene-styrene (SEBS) copolymer, etc.), styrene-acrylonitrile-ethylene-propylene-ethylidene norbornene copolymer (AES), etc.], or water thereof Additives and the like. Particularly preferable styrene resins include polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and styrene-ethylene-butylene-styrene (SEBS) copolymer. More preferred are polystyrene (GPPS) and acrylonitrile-styrene copolymer (AS resin). These styrenic resins can be used alone or in combination of two or more.

In the resin component, the ratio of the styrenic resin is 1 to 40% by weight, preferably 5 to 40% by weight, more preferably 10 to 35% by weight, and still more preferably 12 to 30% in the resin component (A). % By weight. If it is less than 1% by weight, the effect of suppressing the bleed-out of the flame retardant is reduced. If it is 40% by weight or more, it is difficult to ensure flame retardancy, and mechanical strength and the like are further reduced.

Among the (A-2) polystyrene resins in the present invention, an epoxy-modified polystyrene resin is preferably used as a polystyrene resin having good dispersibility and simultaneously improving hydrolysis resistance. Epoxy-modified polystyrene resins are those in which an epoxy group is introduced into a styrene resin. As a method for introducing the epoxy group, any conventionally known method can be used. Specifically, a styrene resin obtained by graft polymerization or copolymerization of an epoxy group-containing vinyl monomer is preferably used. Epoxy group-containing vinyl monomers are compounds that share both radically polymerizable vinyl groups and epoxy groups in one molecule. Specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and itaconic acid. Examples thereof include glycidyl esters of unsaturated organic acids such as glycidyl, glycidyl ethers such as allyl glycidyl ether, and the aforementioned derivatives such as 2-methylglycidyl methacrylate. Among them, glycidyl acrylate and glycidyl methacrylate are preferably used. Moreover, these can be used individually or in combination of 2 or more types.

As a method for producing a styrene resin obtained by graft polymerization or copolymerization of an epoxy group-containing vinyl monomer, a generally known method can be adopted. In particular, styrene, or other styrene and other copolymerizable with this can be used. A method of copolymerizing a monomer and an epoxy group-containing vinyl monomer, styrene, or (co) polymer obtained by copolymerizing styrene and other monomers copolymerizable therewith Examples thereof include a method of graft polymerization of a group-containing vinyl monomer. Furthermore, a polymer compound having a structure obtained by block copolymerization or graft copolymerization of a polymer comprising a copolymerizable unsaturated monomer containing an epoxy group with polystyrene, a comb-type polystyrene having an epoxy group added thereto, and an epoxy group added thereto. Examples thereof include polystyrene. Such copolymerization and graft polymerization can also be performed by known methods.

Examples of the other monomer copolymerizable with styrene include aromatic vinyl compounds other than styrene, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, maleimide monomers, and the like. Examples of the aromatic vinyl compound other than styrene include α-methylstyrene, vinyltoluene, and divinylbenzene. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and (meth) acrylic acid. Examples of the alkyl ester include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and stearyl acrylate. Examples of the maleimide monomer include N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and derivatives thereof. Other examples include diene compounds, maleic acid dialkyl esters, allyl alkyl ethers, unsaturated amino compounds, and vinyl alkyl ethers. These can be used alone or in combination of two or more.

Preferable specific examples of the styrene resin used as a base when the epoxy group-containing vinyl monomer is graft-polymerized or copolymerized with the polystyrene resin by a radical generator or the like include polystyrene resin, high impact polystyrene resin, etc. Resin consisting mainly of polystyrene, acrylonitrile / styrene copolymer (AS resin), styrene / (meth) acrylic acid ester, styrene copolymer such as styrene / butadiene resin, styrene / butadiene / styrene resin, styrene / isoprene / Styrene resin, block copolymer containing styrene such as styrene / ethylene / butadiene / styrene resin, ABS resin such as acrylonitrile / butadiene / styrene resin, acrylonitrile / butadiene / methyl methacrylate / styrene resin And the like. Among these, a resin mainly composed of polystyrene and a styrene copolymer are preferable, and an acrylonitrile / styrene copolymer is most preferable.

The copolymer structure of the polymer having an epoxy group and the polystyrene polymer is not particularly limited. For example, it is a polymer composed of a copolymerizable unsaturated monomer having an epoxy group in the main chain. Comb-shaped polymer compound whose side chain is polystyrene, polymer compound composed of a copolymerizable unsaturated monomer containing an epoxy group and a block-copolymerized linear polymer compound, the main chain is polystyrene A polymer compound having a comb structure, which is a polymer composed of a copolymerizable unsaturated monomer having an epoxy group in the side chain, and a comb having an polystyrene group containing an epoxy group in the main chain and having a side chain made of polystyrene Examples thereof include a polymer compound having a mold structure, polystyrene having a small amount of an epoxy group added thereto, and the like. Among them, a polymer composed of a copolymerizable unsaturated monomer containing an epoxy group in the main chain and having a comb-shaped structure in which the side chain is polystyrene, a polystyrene containing an epoxy group in the main chain and the side A polymer compound having a comb structure in which the chain is polystyrene and a modified polystyrene having a small amount of an epoxy group added are preferred, and in particular, a polymer comprising a copolymerizable unsaturated monomer containing an epoxy group in the main chain and having a side chain A polymer compound having a comb structure in which is a polystyrene is preferable. These polystyrene-based resins containing epoxy groups may be a blend of a plurality of types.

The epoxy group content in the epoxy-modified polystyrene resin is not particularly limited as long as it is effective for improving the compatibility between the (A-1) polyalkylene terephthalate resin and the epoxy-modified styrene resin. The epoxy group-containing monomer is preferably 0.05% by weight or more with respect to the modified polystyrene resin. When copolymerized in a large amount, there is a tendency for fluidity reduction and gelation, and depending on the content of the epoxy group-containing monomer, (A) in the resin component, preferably 40% by weight or less, more preferably 35% by weight or less, More preferably, it is 30 weight% or less.

One or more of these epoxy-modified polystyrene resins can be used. Mixing an epoxy-modified polystyrene resin with a polystyrene resin not containing an epoxy group is also an effective means for adjusting the epoxy group content, molecular weight, and the like.

In the present invention, the content of the styrene component (styrene residue) of the epoxy-modified styrene resin is preferably 50% by weight or more, more preferably 70% by weight in the case of the above-mentioned polystyrene resin mainly composed of styrene. In the case of a styrene copolymer, it is preferably 30% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight or more, and in the case of an ABS resin, 30% by weight or more. More preferably, it is 40% by weight or more, and in the case of a block copolymer, it is 10% by weight or more, more preferably 20% by weight or more.

Examples of the epoxy-modified polystyrene resin obtained by graft polymerization or copolymerization of the epoxy group-containing vinyl monomer include styrene, styrene and other monomers copolymerizable therewith, and epoxy group-containing vinyl monomers. A copolymerized polymer is preferably used.

Among these, an epoxy-modified AS resin obtained by copolymerizing styrene, acrylonitrile and glycidyl methacrylate is particularly preferably used. The amount of glycidyl methacrylate copolymerized in such an epoxy-modified AS resin is not particularly limited as long as it is effective for improving the compatibility with the component (A), but is 0.05% by weight in the epoxy-modified AS resin. The above is preferable. Copolymerization in a large amount tends to decrease fluidity and gelation, and is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less. The copolymerization amount of styrene and acrylonitrile is not particularly limited, but is preferably 50 to 99.9% by weight of styrene, 0.05 to 49.95% by weight of acrylonitrile, 70 to 99.9% by weight of styrene, Acrylonitrile is preferably 0.05 to 29.95% by weight.

The amount of the epoxy-modified polystyrene resin added is preferably 5 to 40 parts by weight, particularly preferably, in the resin component (A) from the viewpoint of the appearance and flame retardancy of the resulting flame-retardant resin composition. Is 10 to 35 parts by weight.

(A-3) Compatibilizing agent In the present invention, a compatibilizing agent may be added. In the resin component of the present invention, the polyalkylene terephthalate resin of a polystyrene-based resin has a subtle effect on flame retardancy and tracking characteristics, and is preferably dispersed in fine particles, but with a polyalkylene terephthalate resin such as an epoxy group. In the case of a polyester resin having no reactive group, it may be difficult to perform good dispersion. Accordingly, when a resin composition is produced, if mechanically dispersed by strong shearing, heat generation causes troubles such as decomposition of the flame retardant, so it is preferable to add a small amount of a compatibilizing agent. A preferable compatibilizer is an epoxy compound. Examples of the epoxy compound used in the present invention include bisphenol-type epoxy compounds, resorcin-type epoxy compounds, novolac-type epoxy compounds, alicyclic compound-type diepoxy compounds, glycidyl ethers, epoxidized polybutadiene, epoxy-modified thermoplastic resins, and epoxy flame retardants. Etc. More specifically, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, resorcinol type epoxy compounds, novolac type epoxy compounds, alicyclic compound type epoxy compounds such as vinylcyclohexene dioxide and dicyclopentadiene oxide, ethylene-glycidyl methacrylate A copolymer and an epoxy oligomer of tetrabromobisphenol A are preferably used. As an epoxy compound used in the present invention, a novolak type epoxy resin having an epoxy equivalent of 150 to 280 g / eq or a bisphenol A type epoxy resin having an epoxy equivalent of 600 to 3000 g / eq is used from the viewpoint of hydrolysis resistance and dispersion in the resin. Preferably used. More preferred is a novolak type epoxy resin having an epoxy equivalent of 180 to 250 g / eq and a molecular weight of 1000 to 6000, or a bisphenol A type epoxy resin having an epoxy equivalent of 600 to 3000 g / eq and a molecular weight of 1200 to 6000.

The compounding quantity of an epoxy compound is 0-10 weight% in (A) resin component, More preferably, it is 0.2-8 weight%. Addition of an epoxy compound is preferred because the dispersibility tends to be improved. When it exceeds 10 weight%, fluidity | liquidity will fall and a flame retardance will fall.

(B) Flame retardant combination In the present invention, the flame retardant combination includes (B-1) a phosphate ester flame retardant, (B-2) a nitrogen flame retardant, (B-3) a borate metal salt and ( B-4) Combination of fluororesins. The content of the phosphorus-based flame retardant is 25 to 55 parts by weight, preferably 15 to 30 parts by weight in the flame retardant combination. By making it within this range, V-0 can be expressed in the UL94 test. The content of the nitrogen-based flame retardant is 30 to 70 parts by weight, preferably 35 to 60 parts by weight in the flame retardant combination. If it is 70 parts by weight or more, the mechanical strength is lowered. The content of the boric acid metal salt is 1 to 20 parts by weight, preferably 1 to 18 parts by weight in the flame retardant combination. By making it within this range, V-0 can be expressed in the UL94 test. The content of the fluororesin is 0.5 to 10 parts by weight, preferably 0.5 to 8 parts by weight in the flame retardant combination. By making it within this range, V-0 can be expressed in the UL94 test.
In the resin composition of the present invention, the flame retardant combination is contained in a proportion of 50 to 130 parts by weight, more preferably 50 to 100 parts by weight, with respect to 100 parts by weight of the resin component (A). If it exceeds 130 parts by weight, the CTI and glow wire characteristics will be reduced, and more gas will be generated. If it is less than 50 parts by weight, flame retardancy, tracking characteristics and glow wire properties cannot be satisfied.
Furthermore, the blending ratio of (B-1) phosphorus flame retardant and (B-2) nitrogen flame retardant is preferably in the range of 0.14 to 1.1, and in the range of 0.14 to 1.0. It is more preferable that By setting it as such a range, CTI and a glow wire characteristic can be improved further.
Further, in the present invention, other flame retardants may be included within the scope not departing from the gist of the present invention, but the content of the halogen-based flame retardant is 5% by weight or less of the content of the flame retardant combination. Preferably, it is 3% by weight or less. The halogen-based flame retardant referred to in the present invention refers to (B-4) a flame retardant containing a halogen other than a fluororesin, and is usually a brominated flame retardant.

(B-1) Phosphate ester compound The component (B-1) phosphate ester compound used in the present invention includes a wide range of phosphate esters. Specific examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate. , Trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, and the like, among which the compound represented by the following general formula (1) is preferable.

In formula, R < ¹ > -R < ⁸ > shows a hydrogen atom or a C1-C6 alkyl group each independently, and m is 0 or an integer of 1-4. R ⁹ is a p-phenylene group, m-phenylene group, 4,4′-biphenylene group or a divalent group selected from the following.

In general formula (1), R ^{1 to} R ⁸ are preferably an alkyl group having 6 or less carbon atoms, and more preferably an alkyl group having 2 or less carbon atoms, in order to improve the hydrolysis resistance of the resin composition used in the present invention. Groups, in particular methyl groups, are preferred. m is preferably an integer of 1 to 3, and 1 is more preferable. When m is 2 or more, the respective —O—R ⁹ —OP— moieties may be the same or different. R ⁹ is preferably a p-phenylene group or an m-phenylene group, and more preferably an m-phenylene group.

Among such phosphate ester compounds, the following compounds (3) and (4) are preferable, and the compound (3) is particularly preferable.

このようなリン酸エステル化合物の市販品としては、大八化学社製ＰＸ−２００、ＰＸ−２０１、ＰＸ−１３０、ＣＲ−７３３Ｓ、ＴＰＰ、ＣＲ−７４１、ＣＲ７４７、ＴＣＰ、ＴＸＰ、ＣＤＰから選ばれる１種または２種以上が使用することができ、好ましくはＰＸ−２００、ＴＰＰ、ＣＲ−７３３Ｓ、ＣＲ−７４１、ＣＲ７４７から選ばれる１種または２種以上、特に好ましくはＰＸ−２００、ＣＲ−７３３Ｓ、ＣＲ−７４１を使用することができるが、この中で特に好ましくはＰＸ−２００である。
また、下記式（５）で表される芳香族ホスフェート化合物も好ましく使用できる。

As a commercial item of such a phosphoric ester compound, it is selected from Daihachi Chemical Co., Ltd. PX-200, PX-201, PX-130, CR-733S, TPP, CR-741, CR747, TCP, TXP, CDP. 1 type or 2 types or more can be used, Preferably it is 1 type or 2 or more types chosen from PX-200, TPP, CR-733S, CR-741, CR747, Especially preferably, PX-200, CR-733S CR-741 can be used, among which PX-200 is particularly preferable.
Moreover, the aromatic phosphate compound represented by following formula (5) can also be used preferably.

（式中、Ｒ¹、Ｒ²、Ｒ⁴、Ｒ⁵は、それぞれ、水素原子または炭素数３０以下の、アルキル基、アルケニル基、アリール基、アルキルアリール基若しくはアリールアルキル基を表し、Ｒ³は、２官能基を有するナフタレン環を表し、ｎは、１〜５の整数を表す。）
式（５）で表される芳香族ホスフェート化合物の中でも１, ５−ナフタレンビスジフェニルリン酸エステルが好ましい。

(Wherein R ¹ , R ² , R ⁴ and R ⁵ each represents a hydrogen atom or an alkyl group, alkenyl group, aryl group, alkylaryl group or arylalkyl group having 30 or less carbon atoms, and R ³ represents A naphthalene ring having a bifunctional group is represented, and n represents an integer of 1 to 5.)
Among the aromatic phosphate compounds represented by the formula (5), 1,5-naphthalene bisdiphenyl phosphate is preferable.

(B-2) Salts of amino group-containing triazines In the salt of amino group-containing triazines which are nitrogen-based flame retardants, the amino group-containing triazines (triazines having an amino group) are usually amino group-containing 1, 3,5-triazines are used. For example, melamine, substituted melamine (2-methylmelamine, guanylmelamine, etc.), melamine condensate (melam, melem, melon, etc.), melamine co-condensation resin (melamine-formaldehyde resin resin) Etc.), cyanuric acid amides (ammeline, ammelide, etc.), guanamine or its derivatives (guanamine, methylguanamine, acetoguanamine, benzoguanamine, succinoguanamine, adipoguanamine, phthaloguanamine, CTU-guanamine, etc.).

Examples of the salt include salts of the triazines with inorganic acids and organic acids. Inorganic acids include nitric acid, chloric acid (such as chloric acid and hypochlorous acid), phosphoric acid (such as phosphoric acid exemplified in the above-mentioned metal hydrogen phosphate section), sulfuric acid (non-condensed sulfuric acid such as sulfuric acid and sulfurous acid, And condensed sulfuric acid such as peroxodisulfuric acid and pyrosulfuric acid), boric acid, chromic acid, antimonic acid, molybdic acid, tungstic acid and the like. Of these, phosphoric acid and sulfuric acid are preferred. Organic acids include organic sulfonic acids (aliphatic sulfonic acids such as methanesulfonic acid, aromatic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid), cyclic ureas (uric acid, barbituric acid, cyanuric acid, acetylene urea, etc.) ) And the like. Of these, alkane sulfonic acids having 1 to 4 carbon atoms such as methanesulfonic acid, arenesulfonic acids having 6 to 12 carbon atoms such as toluenesulfonic acid, and cyanuric acid are preferable.

Examples of salts of amino group-containing triazines include melamine phosphates (melamine polyphosphate, melamine polyphosphate, melam, melem double salt, etc.), melamine sulfates (melamine sulfate, dimelamine sulfate, dimelam pyrosulfate), sulfone, etc. Melamines (Melamine methanesulfonate, melam methanesulfonate, melem methanesulfonate, melamine methanesulfonate, melam melem, double salt, melamine toluenesulfonate, melam toluenesulfonate, melamine toluene, melam memel double salt) Etc.). These salts of amino group-containing triazines can be used alone or in combination of two or more.

Among such nitrogen-based flame retardants, those preferably used in the present invention are cyanuric acid or an adduct of isocyanuric acid and a triazine-based compound, usually 1 to 1 (molar ratio), sometimes 1 to 1 pair. It is an adduct having a composition of 2 (molar ratio). More specifically, they are melamine cyanurate, benzoguanamine cyanurate, acetoguanamine cyanurate, and further melamine cyanurate. These salts are produced by a known method. For example, a mixture of a triazine compound and cyanuric acid or isocyanuric acid is made into a water slurry and mixed well to form both salts in the form of fine particles. Is generally obtained in the form of a powder after filtration and drying. The salt does not need to be completely pure, and some unreacted triazine compound, cyanuric acid, or isocyanuric acid may remain. In addition, the average particle size of the salt before blending with the resin is preferably 100 to 0.01 μm, more preferably in terms of flame retardancy, mechanical strength, heat and humidity resistance, residence stability, and surface properties of the molded product. Is 80-1 μm. In addition, when the dispersibility of the salt is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate, a known surface treatment agent, or the like may be used in combination.

In the (B) flame retardant combination, the composition ratio (weight ratio) of the (B-1) phosphorus flame retardant and (B-2) nitrogen flame retardant is preferably (B-1) / (B-2). ) = 0.14 to 1.1, more preferably 0.2 to 1.0, and still more preferably 0.3 to 0.95. When the component ratio is 0.14 or more, flame retardancy tends to be further improved, and when it is 1.1 or less, the GWIT value can be further improved.

(B-3) Metal borate The polyester resin composition of the present invention preferably contains (B-3) a metal borate. The component (B-3) boric acid metal salt used in the present invention is preferably stable under normal processing conditions and free from volatile components. Examples of the boric acid metal salt include alkali metal salts of boric acid (for example, sodium tetraborate, potassium metaborate, etc.) or alkaline earth metal salts (for example, calcium borate, magnesium orthoborate, barium orthoborate, zinc borate, etc.). Among these, zinc borate is preferable. Zinc borate is generally represented by 2ZnO.3B ₂ O ₃ .xH ₂ O (x = 3.3 to 3.7). The hydrated zinc borate is preferably one having the formula 2ZnO.3B ₂ O ₃ .3.5H ₂ O and stable up to a temperature of 260 ° C. or higher.

The amount of the metal borate is 1 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the component (A). When the compounding amount of the boric acid metal salt exceeds 20 parts by weight, the mechanical properties tend to be lowered.

(B-4) Fluororesin Fluororesin is blended as an anti-dripping agent at the same time as the flame retardant aid, and as the fluororesin, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / Fluorinated polyolefins such as hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, vinylidene fluoride, polychlorotrifluoroethylene, etc. are preferable, among which polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer Polymers, tetrafluoroethylene / hexafluoropropylene copolymers, and tetrafluoroethylene / ethylene copolymers are more preferable, and polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene are more preferable. Pyrene copolymer is more preferred.

The fluororesin preferably has a melt viscosity at 350 ° C. of 1.0 × 10 ^{2 to} 1.0 × 10 ¹⁵ (Pa · s), among which 1.0 × 10 ^{3 to} 1.0 × 10 ¹⁴ (Pa S), in particular, 1.0 × 10 ^{10 to} 1.0 × 10 ¹² (Pa · s) is preferably used. By setting the melt viscosity to 1.0 × 10 ² (Pa · s) or more, the anti-dripping ability during combustion tends to be improved, and by setting the melt viscosity to 1.0 × 10 ¹⁵ (Pa · s) or less, The fluidity of the composition tends to decrease.

The quantity of a fluororesin is 0.5-10 weight part with respect to 100 weight part of component (A), Preferably it is 0.7-8 weight part, More preferably, it is 1-7 weight part. If the amount of the fluororesin is less than 0.5 parts by weight, the effect of preventing dripping during combustion is insufficient, and if it is more than 10 parts by weight, the fluidity and mechanical properties are lowered.

(C) Inorganic filler The resin composition used in the present invention preferably contains (C) an inorganic filler. As fillers, fibrous fillers (glass fiber, carbon fiber, basalt fiber, silica / alumina fiber, zirconia fiber, boron fiber, boron nitride fiber, silicon nitride potassium titanate fiber, etc.), granular filler (kaolin, Examples thereof include silicates such as talc and wollastonite; metal carbonates such as calcium carbonate; metal oxides such as titanium oxide) and plate-like fillers (mica, glass flakes, various metal foils, etc.). Among these fillers, fibrous fillers, particularly glass fibers (such as chopped strands) are preferable because they have high strength and rigidity. These fillers can be used alone or in combination of two or more.

These fillers may be used in combination with a sizing agent or a surface treatment agent. Such sizing agents or surface treatment agents include functional compounds. Examples of the functional compound include epoxy compounds, silane compounds, titanate compounds, and the like. The amount of the inorganic filler is 0 to 200 parts by weight, preferably 5 to 150 parts by weight, with respect to 100 parts by weight of the (A) resin component. By setting it as such a range, there exists an effect of expressing a high-strength fiber physical property.

In the resin composition used in the present invention, the content of each of the polyphenylene ether resin, polyphenylene sulfide resin, phenolic resin and red phosphorus is 1% by weight or less, and more preferably 0.8% by weight or less. When any of these components is more than 1% by weight, there is a problem that CTI is lowered.

In the polyalkylene phthalate resin composition used in the present invention, a conventional additive and the like can be blended in addition to the above components within the range not departing from the gist of the present invention. There are no particular restrictions on the additives to be added. For example, additives such as antioxidants, heat stabilizers, lubricants, mold release agents, catalyst deactivators, crystal nucleating agents, crystallization accelerators, It can be added during or after the polymerization of the alkylene terephthalate resin. An epoxy compound, carbodiimide, oxazoline, or the like can be added to further improve the hydrolysis resistance. Furthermore, in order to impart desired performance to polyalkylene terephthalate, stabilizers such as UV absorbers and weathering stabilizers, colorants such as dyes and pigments, antistatic agents, foaming agents, plasticizers, impact modifiers. Etc. can be blended.

Furthermore, in the polyalkylene terephthalate resin composition used in the present invention, a resin other than the polyalkylene terephthalate resin can be blended as necessary within a range not impairing the object of the present invention. However, as described above, the blending of polyphenylene ether resin, polyphenylene sulfide resin, and phenol resin is not preferable because it decreases the tracking characteristics, and it is necessary to suppress the content within 1% by weight in the total resin composition. Here, the polyphenylene ether resin and polyphenylene sulfide resin disclosed in Patent Document 8 and the phenol resin disclosed in Patent Document 6 are applied in the present invention.
Polyolefin resins such as polyethylene and polypropylene have the effect of improving tracking characteristics, but significantly reduce flame retardancy. These thermoplastic resins and thermosetting resins can be used alone or in combination of two or more.

The production method of the flame-retardant polyalkylene terephthalate resin composition of the present invention is not particularly limited, and can be easily achieved by mixing each component by a known method. For example, a dry blending method using a blender or a mixer, a melt mixing method using an extruder, and the like can be mentioned. Usually, a screw extruder is used to melt and extrude a strand to form a pellet. The method is suitable. Specifically, a method of melting and kneading each component at once, a method of first melting and mixing a specific component, and the like, among others, from the viewpoint of mechanical properties, a resin component (A) and a flame retardant combination component ( A production method is preferred in which B) is first melt mixed and then the remaining components are mixed.

The mixing method of each component is not particularly limited, and a batch blending method in which components are melted and kneaded at once using a twin screw extruder, and split blending in which reinforcing fillers are added from other supply ports The method etc. are mentioned.

There is no particular limitation on the molding method of the polyalkylene terephthalate molded product of the present invention, and molding methods generally used for thermoplastic resins, that is, molding methods such as injection molding, hollow molding, extrusion molding, press molding, etc., are applied. Particularly preferred molding method is injection molding because of its good fluidity. In the injection molding, the resin temperature is preferably controlled to 240 to 280 ° C.

The insulating material part of the present invention has a resin molded part formed using the polyalkylene terephthalate resin composition, and the resin molded part directly supports a connection part through which a rated current exceeding 0.2 A flows. Or at a distance of 3 mm or less from these connections. Here, “the resin molded part directly supports a connection part through which a rated current exceeding 0.2 A flows” means that the contact is a connection part. Also, “the resin molded part is within a distance of 3 mm from the connection part through which the rated current exceeding 0.2 A flows” means that, for example, in the case of relay parts, the connection part (contact) is inscribed inside the resin molded part. This represents a case where a space of several millimeters is provided between the contact point and the resin molding part. Even in such a case, high electrical safety is still necessary, and the present invention is effective.

Moreover, the thickness of the resin formation part in the insulating material component of this invention can be suitably determined according to the use etc. of this insulating material component. For example, the insulating material component of the present invention may have a thin portion having a thickness of 2 mm or less. Further, the shape of the resin forming portion is not particularly defined, and a plate shape, a spherical shape or the like can be widely adopted.

Insulating material parts of the present invention are excellent in flame retardancy, mechanical properties, etc., have no mold corrosion due to the generation of corrosive gas, and have low specific gravity and fluidity, so applications that require thin walls or complex shapes Can also be widely adopted. For example, the material which manufactures an electric equipment, an electronic device, or those components is mentioned.

Even if the insulating material component of the present invention is a component that requires high electrical safety, it has a high GWFI value (for example, 850 ° C. or more at a thickness of 1.5 mm) and a high GWIT value (for example, at a thickness of 0.8 to 3 mm). 775 ° C. or higher) and can satisfy the requirements of flame retardancy (eg, V-0) and high PTI (eg, 550 V or higher) of UL standards, which have been conventionally required. Therefore, it is preferable.

The insulating material component of the present invention is preferably used as a contact electrical / electronic component selected from the group consisting of relays, switches, connectors, sensors, actuators, microswitches, microsensors and microactuators by combining with metal contacts, copper plates, etc. be able to.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

In Examples and Comparative Examples, evaluation of measurement of physical properties of resins was performed by the following methods.

(1) Terminal carboxyl group amount;
Polybutylene terephthalate (0.1 g) was dissolved in 3 ml of benzyl alcohol, and titrated with a 0.1 mol / liter-benzyl alcohol solution of sodium hydroxide.

(2) Temperature drop crystallization temperature;
Using a differential scanning calorimeter [Perkin Elmer, Model 1B], polybutylene terephthalate was heated from room temperature to 300 ° C. at a temperature increase rate of 20 ° C./min, and then decreased to 80 ° C. at a temperature decrease rate of 20 ° C./min. In this case, the temperature of the exothermic peak was measured and used as the temperature lowering crystallization temperature.

(3) residual tetrahydrofuran amount;
5 g of polybutylene terephthalate pellets were immersed in 10 g of water, treated under pressure at 120 ° C. for 6 hours, and tetrahydrofuran eluted in water was quantified by gas chromatography.

(4) Intrinsic viscosity;
Using a mixed solvent of Ubbelohde viscometer and phenol / 1,1,2,2-tetrachloroethane (weight ratio 1/1), at 30 ° C., concentrations of 1.0 g / dl, 0.6 g / dl and 0.3 g The viscosity of the / dl solution was measured and the viscosity number was extrapolated to zero concentration.

Each component used in the examples and comparative examples is as follows.
[raw materials]
(A-1a) PBT-1 resin: Polybutylene terephthalate resin produced by the following continuous polymerization method, the amount of terminal carboxyl groups is 20 eq / t, the temperature-falling crystallization temperature is 178 ° C., and the amount of residual tetrahydrofuran is 180 ppm ( Weight ratio) and intrinsic viscosity was 0.85 dl / g.
[PBT-1 production method]
Both raw materials were supplied to a slurry preparation tank at a ratio of 1.8 mol of 1,4-butanediol with respect to 1.0 mol of terephthalic acid, and 2,972 parts by weight of slurry prepared by mixing with a stirrer (terephthalic acid 9 0.06 mol part, 1,4-butanediol 16.31 mol part) continuously adjusted to a temperature of 230 ° C. and a pressure of 101 kPa by a gear pump, transferred to the first esterification reaction tank, and tetrabutyl titanate 3 .14 parts by weight was supplied, and the esterification reaction was conducted with stirring for 2 hours to obtain an oligomer. From the first esterification reaction tank, the oligomer was transferred to a second esterification reaction tank adjusted to a temperature of 240 ° C. and a pressure of 101 kPa, and the esterification reaction was further advanced with stirring for 1 hour. The oligomer is transferred from the second esterification reaction tank to the first polycondensation reaction tank adjusted to a temperature of 250 ° C. and a pressure of 6.67 kPa, and subjected to a polycondensation reaction with stirring for 2 hours to obtain a prepolymer. It was. From the first polycondensation reaction tank, the prepolymer was transferred to a second double condensation reaction tank adjusted to a temperature of 250 ° C. and a pressure of 133 Pa, and the polycondensation reaction was further advanced with stirring for 3 hours to stir the polymer. Obtained. The polymer was extracted from the second double condensation tank, transferred to a die, drawn into a strand, and cut with a pelletizer to obtain a beret-like polybutylene terephthalate.

(A-1b) PBT resin: Polybutylene terephthalate resin produced by the following batch polymerization method, the amount of terminal carboxyl groups is 41 eq / t, the temperature-falling crystallization temperature is 170 ° C., and the amount of residual tetrahydrofuran is 680 ppm (weight ratio) ), And the intrinsic viscosity was 0.85 dl / g.
[PBT-2 production method]
The polymerization reaction was carried out using a batch apparatus. A total of 3,226 parts by weight is supplied to the transesterification reactor at a ratio of 1.8 moles of 1,4-butanediol to 1.0 mole of dimethyl terephthalate, and 3.14 parts by weight of tetrabutyl titanate is added. Then, an ester exchange reaction was performed at a temperature of 210 ° C. and a pressure of 101 kPa for 3 hours to obtain an oligomer. Subsequently, this oligomer was transferred to a polycondensation reaction tank, and under agitation, a polycondensation reaction was carried out at a temperature of 250 ° C. and a pressure of 133 Pa for 3 hours to obtain a polymer. Next, nitrogen pressure was applied to extract the strands, and the pellets were cut with a pelletizer to obtain pellets of polybutylene terephthalate.

(A-1c) PET resin: Polyethylene terephthalate resin (trade name Novapet PBK1 manufactured by Mitsubishi Chemical Corporation).

(A-2a) Epoxy-modified AS resin: AS resin (manufactured by Technopolymer Co., Ltd., Sanrex SAN-C, melt mass flow rate 25 g / 10 min PS / AN = 75/25 (weight ratio)) to 100 parts by weight , 3 parts by weight of glycidyl methacrylate and 0.015 parts by weight of 2.5-dimethyl-2.5-di- (tert-butylperoxy) hexyne, and 210 ° C. using a 30 mm twin screw extruder And kneaded in pellets. After unreacted glycidyl methacrylate was extracted with acetone, the amount of glycidyl methacrylate was quantified by measuring the ultraviolet absorption spectrum, and it was confirmed that the reaction was 1.7% by weight.

(A-2b) EGMA-g-PS: Epoxy-modified polystyrene resin, manufactured by Nippon Oil & Fats Co., Ltd., trade name Modiper A4100 (comb-type structural polymer obtained by grafting polystyrene to an ethylene-glycidyl methacrylate copolymer. EGMA / PS = 70 / 30% by weight).

(A-2c) AS resin: Styrene-acrylonitrile copolymer resin, manufactured by Technopolymer Co., Ltd., Sanrex SAN-C, melt mass flow rate 25 g / 10 min, PS / AN = 75/25.

(A-2d) PS resin: GPPS resin, manufactured by PS Japan, trade name HF77, melt flow rate 7.5 g / 10 min.

(A-3) Epoxy compound: bisphenol A type epoxy resin as a compatibilizer, manufactured by Asahi Denka Kogyo Co., Ltd., trade name Adeka Sizer EP17

(B-1) Phosphate ester compound: manufactured by Daihachi Chemical Co., Ltd., trade name PX200
Phosphate ester represented by the following formula (6).

(B-2) Triazine ring-containing compound: Melamine cyanurate (manufactured by Mitsubishi Chemical Corporation, trade name MX44).

(B-3) Zinc borate: Borax Japan Co., Ltd., trade name Firebreak ZB).
(B-4) PTFE: polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., tetrafluoroethylene resin, polyflon F201).

(C) GF: Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., epoxysilane-treated product, 3 mm chopped strand, brand name: T-187H).

(D-1) Brominated flame retardant: Brominated polystyrene (Albemarle Japan Co., Ltd., trade name Saytex HP-7010).
(D-2) Antimony compound: antimony trioxide (manufactured by Moriroku Co., Ltd., trade name MIC-3).
(D-3) Epoxysilane treatment ME100: ME100 (Coop Chemical Co., Ltd., swellable synthetic mica) subjected to an epoxy group addition treatment.
(D-4) Magnesium hydroxide: Kyowa Chemical Industry Co., Ltd., trade name KISUMA 120.

(E) Stabilizer: A hindered phenol-based compound (Ciba Specialty Japan Co., Ltd., trade name: Irganox 1010).
(F) Release agent: calcium montanate (manufactured by Clariant Japan Co., Ltd., trade name CaV102).

(G-1) PPE resin: Polyphenylene ether resin (Mitsubishi Engineering Plastics Co., Ltd., trade name Iupiace, intrinsic viscosity 0.36).
(G-2) Phenol resin: Novolak phenol resin (manufactured by Sumitomo Durez Co., Ltd., trade name Sumilite Resin PR-53195).
(G-3) Red phosphorus: Red phosphorus surface-coated with a phenol resin (Rin Chemical Industry Co., Ltd., trade name Nova Excel 140: Red phosphorus content 95%).

[Performance evaluation method]
(1) Flame Retardancy Test UL test pieces (thickness 1/32 inch) were conducted by the UL-94 standard vertical combustion test of Underwriter's Laboratories Inc. The flame retardancy level is evaluated in the order of V-0>V-1>V-2> HB in accordance with the standard, and flame retardancy of V-2 or higher is required, preferably V-0.

(2) Proof Tracking Index test (abbreviation: PTI test)
For the test piece (a flat plate having a thickness of 3 mm), the PTI was determined by the test method defined in the international standard IEC60112. This PTI is a numerical value of the guaranteed voltage in increments of 25V. PTI exhibits resistance to tracking at a voltage between 600V and 100V when wet-contaminated with an electric field applied to the surface of the solid electrical insulating material, and usually requires 550V or more, preferably 600V. That's it.

(3) Glow-wire Flammability Index test (abbreviation: GWFI test)
The test method (flat plate with a thickness of 3 mm) was subjected to the test method defined in IEC60695-2-12. That is, a red hot rod having a predetermined shape (a nickel / chromium (80/20) wire having an outer diameter of 4 mm in a loop shape) is brought into contact for 30 seconds and then pulled apart. It is defined as the maximum temperature at the tip that does not ignite during this time or extinguishes within 30 seconds after being disengaged, and tests up to 960 ° C. 850 ° C. or higher is required for flame retardant applications. In this invention, it was determined whether it passed at 960 degreeC.

(4) Glow-wire Ignition Temperature test (abbreviation: GWIT test)
Three types of flat plate test pieces having thicknesses of 0.75 mm, 1.5 mm, and 3 mm were subjected to the test method defined in IEC 60695-2-13. That is, it is defined as a temperature that is 25 ° C. higher than the highest temperature at the tip that does not ignite when a red hot rod having a predetermined shape (a nickel / chromium (80/20) wire having an outer diameter of 4 mm in a loop shape) is contacted for 30 seconds. For flame-retardant applications, a GWIT value of 0.8 to 3 mm thickness is required to be 775 ° C. or higher. More preferably, 800 ° C. or higher is required.

(5) Flame retardant bleed out test Using a 10 cm square flat plate with a thickness of 3 mm as a sample, heat treatment was performed for 48 hours in a hot air dryer controlled at 150 ° C., and then the surface of the test piece was difficult to observe by visual observation. The exudation of the fuel was classified into the following four stages. ◎ and ○ are practically usable levels.
A: No exudation ○: Exudation is slightly observed Δ: Exudation occurs x: Exudation is large.

(6) Tensile test An ISO tensile test piece (ISO 3167) was used and measured according to ISO 527.

(7) Hydrolysis resistance test The ISO tensile test piece was wet-heat treated in saturated steam at a temperature of 121 ° C for 40 hours. About the ISO test piece before and behind a process, the tensile test was done based on ISO527 and the tensile strength retention was measured.

(8) Place 5 g of the generated gas resin composition pellets in a glass vial with an internal volume of 26 ml, heat at 150 ° C. for 2 hours, collect a sample from the gas phase using a microsyringe, and analyze by gas chromatography did. The peak area of the chromatogram was obtained, and the weight of tetrahydrofuran corresponding to the area was expressed as a ratio (ppm) to the resin.

[Examples 1-8 and Comparative Examples 1-16]
Ingredients other than the glass fibers shown in Table 1 or Table 2 are mixed together with a super mixer (SK-350 type, manufactured by Shinei Machinery Co., Ltd.), and L / D = 42 twin screw extruder (manufactured by Nippon Steel Works, TEX30HSST). ), The glass fiber was side-feeded, and extruded under conditions of a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, and a barrel temperature of 260 ° C. to obtain a pellet of a polyalkylene terephthalate resin composition. .
About the resin composition pellet, using the injection molding machine (manufactured by Sumitomo Heavy Industries, Model SH-100), the tests of (1) to (5) above under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C. Pieces (three kinds of flat plate test pieces each having a length and width of 10 cm and thicknesses of 0.75 mm, 1.5 mm and 3 mm, and a test piece of UL-94 standard having a thickness of 1/32 inch) were manufactured. Moreover, as a test piece of the above (6) tensile test and (7) hydrolysis resistance test, an injection molding machine (model S-75 MIII manufactured by Sumitomo Heavy Industries, Ltd.) was used and the ISO tensile test was performed at 265 ° C. A test piece (ISO 3167) was molded. Said evaluation was implemented using the above test piece. The pellets of the resin composition were dried with hot air at 120 ° C. for 8 hours, and (8) the amount of generated gas was measured. The evaluation results are shown in Table 1 or Table 2.

From Tables 1 and 2, the following is clear.
(1) Comparative Example 1 in which a brominated flame retardant and an antimony compound are blended has a low PTI and does not reach 775 V at a thickness of 0.75 mm and 1.5 mm of 1 GWIT value, which is extremely limited in the range of use of parts. Was confirmed to exist.
(2) The flame retardant bleed out was remarkable in the comparative example 3 which mix | blended the flame retardant combination as usual and did not mix | blend the polystyrene-type resin of (A-2) component. On the other hand, it was found that in Comparative Example 6 in which the blending amount of the polystyrene-based resin was excessive and in Comparative Example 7 in which the amount of the flame retardant combination was small, the flame retardancy and electrical safety were lowered.
(3) It was found that Comparative Example 8 in which the blending amount of the flame retardant combination is excessive has high flame retardancy but low initial physical properties. Moreover, it turned out that the comparative example 9 in which the composition ratio of a flame retardant combination does not fall within the scope of the present invention is low in flame retardancy and electrical safety.
(4) Comparative Example 4 and Comparative Example 5 similar to the composition of Example 3 of Patent Document 5 and Example 10 of Patent Document 4 ensure flame retardancy, although no bleed out due to the flame retardant is observed. Therefore, it was found that the amount of the flame retardant increases, so that tracking and glow wire properties are slightly lowered.
(5) In Examples 1 to 8 within the scope of the present invention, the flame retardancy is also V-0, the PTI is 550 V, the GWFI value at 960 ° C. is acceptable, and the GWIT value is also 0.75 to 3.0 mm thick. It was proved that the electrical safety was extremely high at 775 V or more in all the ranges. In addition, it was found that there is little bleed out due to the flame retardant, the mechanical strength is in a practically sufficient range, and the hydrolysis resistance is also good.
(5) In Example 1 based on PBT resin with a small amount of terminal carboxyl groups and residual tetrahydrofuran, the amount of generated gas is remarkably reduced as compared with Example 8 using PBT resin with many characteristics. It was found that it is extremely useful in practical applications for contact parts such as.
(6) From the comparison between Example 1 and Example 7, the GWIT value and the amount of generated gas are further improved by making the blending ratio of the phosphorus-based flame retardant and the nitrogen-based flame retardant more preferable ranges of the present invention. Was confirmed.
(7) In Comparative Example 14 and Comparative Example 15 in which PPE resin or phenol resin was further blended with the composition of Example 1, the flame retardancy and bleed-out property were good, but the tracking property was significantly reduced. It turned out to be unfit for the purpose. Further, Comparative Example 16 in which red phosphorus was further added to the composition of Example 1 had good flame retardancy, bleed-out property, and tracking property, but the molded product was reddish and colored.
(8) In the comparison of Examples 1 to 6 in which various polystyrene resins were blended, the flame retardant bleed-out in Example 2 in which only the component A-2b having a low content of aromatic vinyl monomer was blended was It was confirmed that there were many compared with the Example. On the other hand, it was confirmed that the tracking property of Example 4 in which component A-2d containing only the aromatic vinyl monomer was mixed was slightly lowered as compared with the others.
(9) Examples 3 and 4 containing only a polystyrene-based resin that does not contain an epoxy group have slightly worse glow wire properties and hydrolysis resistance than Examples 1, 2, 5 and 6. At the same time, flame retardancy maintained V-0, but the combustion time was slightly longer.

From the above results, Examples 1 to 8 in Table 1 are IEC 60335-1 standard, insulating material parts supporting connections through which a current exceeding 0.2 A flows during normal operation, and 3 mm from these connections. It was confirmed that it was in conformity with the provisions of insulation material parts within. Therefore, the insulating material part according to the present invention suppresses the bleed-out of the flame retardant, has excellent overall flame retardancy, PTI, GWFI value, GWIT value and mechanical properties, and further has terminal carboxyl groups and residuals. It can be seen that the use of PBT resin with a small amount of tetrahydrofuran is useful for contact parts such as relays with a small amount of generated gas.

The molded article of the present invention is a part of a device that operates in a state where an operator is not attached to a household electric product such as a refrigerator or a fully automatic washing machine, and supports a connection portion through which a current exceeding 0.2 A flows during operation. Insulating material parts and electrical insulating material parts (printed circuit boards, terminal blocks, plugs, etc.) within a distance of 3 mm from these connecting parts are applied to improve electrical safety. Further, it can be seen that the use of a PBT resin with a small amount of terminal carboxyl groups and residual tetrahydrofuran is useful for contacted parts such as relays with a small amount of generated gas. Since the molded article of the present invention is excellent in flame retardancy and improved in electrical safety, it can be used in other electrical / electronic equipment fields, automotive fields, mechanical fields, and the like.

Claims (11)

(A) For 100 parts by weight of a resin component having the following composition ratio,
(A-1) Polyalkylene terephthalate resin 99-50% by weight
(A-2) Polystyrene resin 1 to 40% by weight
(A-3) Compatibilizer 0-10% by weight
(B) The total amount of the following flame retardant combination component is 50 to 130 parts by weight and (B-1) 25 to 55 parts by weight of a phosphoric ester-based flame retardant (B-2) a nitrogen system comprising a salt of an amino group-containing triazine Flame retardant 30 to 70 parts by weight (B-3) Boric acid metal salt 1 to 20 parts by weight (B-4) Fluorine resin 0.5 to 10 parts by weight (C) Inorganic filler 0 to 200 parts by weight And a resin molded part formed using a polyalkylene terephthalate resin composition in which the content of any of polyphenylene ether resin, polyphenylene sulfide resin, phenolic resin and red phosphorus is 1% by weight or less. Insulating material part characterized in that the molded part directly supports the connection parts through which a rated current exceeding 0.2 A flows or is within a distance of 3 mm from these connection parts . (B) In the flame retardant combination, the composition ratio (weight ratio) of (B-1) phosphate ester flame retardant and (B-2) nitrogen flame retardant is (B-1) / (B-2) = 0. The insulating material component according to claim 1, which is in a range of .14 to 1.1. (A-1) The insulating material component according to claim 1 or 2, wherein the main component of the polyalkylene terephthalate resin is a polybutylene terephthalate resin. (A-2) The insulating resin component according to any one of claims 1 to 3, wherein the polystyrene-based resin includes an epoxy-modified polystyrene-based resin. The main component of (A-1) polyalkylene terephthalate resin is a polybutylene terephthalate resin having a terminal carboxyl group amount of 30 eq / t or less and a residual tetrahydrofuran amount of 300 ppm or less. The insulating material part of any one of -4. The insulating material part according to any one of claims 1 to 5, wherein the resin molded portion has a thin portion having a thickness of 2 mm or less. The resin molded portion has a thin portion having a thickness of 2 mm or less, and the insulating material component having the connection portion is disposed in contact with the resin forming portion. Insulating material parts. The shape of the said insulating material component is plate shape, The insulating material component of any one of Claims 1-7 characterized by the above-mentioned. The insulating material component according to claim 1, wherein the connecting portion is a contact point. (A-1) The main component of the polyalkylene terephthalate resin is a polybutylene terephthalate resin having a terminal carboxyl group amount of 30 eq / t or less and a residual tetrahydrofuran amount of 300 ppm or less. Insulating material parts described in 1. The insulating material component according to any one of claims 1 to 10, wherein the insulating material component is a contact electrical / electronic component selected from the group consisting of a relay, a switch, a connector, a sensor, an actuator, a microswitch, a microsensor, and a microactuator. Insulating material parts.